JPH0488050A - Fire retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a fire retardant resin composition having excellent light resistance, heat resistance, practical processability, impact resistance and especially heat stability comprising a rubber-reinforced styrene-based resin, a specific halogen-containing compound, a phosphite-based compound as essential ingredients. CONSTITUTION:(A) 100 pts.wt. rubber-reinforced styrene-based resin containing 5-60wt.% rubber component and having 15-180wt.% grafted ratio and 50-100/0-50 weight ratio of copolymerized aromatic vinyl/cyanated vinyl, or 100 pts.wt. a composition composed of 20-90wt.% the component A and 10-80 wt.% polycarbonate is mixed with (B) 1-30 pts.wt. a compound expressed by formula I (R<1> and R<2> are H or expressed by formula II, etc.; X is Br or Cl; i is 0-4; m is 0-10) and having 45-60 wt.% halogen content, (C) 0.05-5 pts.wt. phosphite-based compound and preferably furthermore 0-20 pts.wt. (except B) halogenated bisphenol-based compound, 0-15 pts.wt. halogenated polyolefin and 0-15 pts.wt. antimony compound to afford the aimed composition.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a light-resistant, heat-resistant, practical molding material containing a rubber-reinforced styrene resin, a specific flame retardant, and a phosphite compound as the main components. The present invention relates to a flame-retardant resin composition having excellent properties, impact resistance, thermal stability, and flame retardancy.

[Prior Art] Rubber-reinforced styrenic resins such as high-impact polystyrene and ABS resins have excellent mechanical properties, electrical insulation properties, moldability, and molded appearance, and are therefore used in automotive parts, electrical It is used in a wide range of industrial products such as equipment parts and building materials.

However, because rubber-reinforced styrene resin is easily flammable, in recent years it has been subject to various laws and regulations regarding flammability from the standpoint of safety, depending on its use. has been done.

In this way, flame-retardant rubber-reinforced styrene resins have come to be widely used as molding materials for various industrial products. Moreover, when these devices are used as exterior decorations, fading due to direct sunlight from windows or indoor fluorescent light has recently become a particular problem, and these materials have excellent light resistance. is an essential condition.

Furthermore, when these materials are used as exterior materials, most of them are large parts, and excellent practical moldability and impact resistance are required.

For this reason, flame-retardant rubber-reinforced styrene-based resins are required to have multifunctional properties that include not only flame retardancy but also excellent light resistance, heat resistance, practical moldability, and impact resistance. has been done. Particularly recently, due to improvements in molding productivity and the development of new applications, flame-retardant rubber-reinforced styrene resins with even better thermal stability than conventional resins have been required.

Conventionally, it was common practice to select the type of flame retardant to provide the above performance, but it has not been possible to obtain a multifunctional flame retardant rubber-reinforced styrene resin that has both of the above properties. It wasn't.

[Issue 8 to be solved by the invention] The present invention has been made against the background of the above-mentioned prior art, and has improved not only flame retardancy but also light resistance, heat resistance, practical moldability, impact resistance, and especially thermal stability. The purpose of the present invention is to provide a flame-retardant resin composition with even better flame retardant properties.

[Means for Solving the Problems] The present invention provides (A) a graft ratio of 15 to 180% by weight, copolymerized aromatic vinyl/vinyl cyanide 50 to 10010 to 50%;
(B) 1 to 30 parts by weight of a norogen-containing compound represented by the following general formula (I) (C) to 100 parts by weight of a rubber-reinforced styrenic resin having a rubber component content of 5 to 60% by weight. Phosphite ester compound 0.05 to 5 parts by weight (D) Halogenated bisphenol compound [However, (B
) components] 0 to 20 parts by weight (E) 0 to 15 parts by weight of a halokenated polyolefin (F) 0 to 15 parts by weight of an antimony compound (hereinafter referred to as "No. 1 composition).

(B)-Sailor (I) CH3 C)-CH2 CH-CH2] H CH3 ・・・・・・・・・・・・・・・・・・・・・ (I)
In the formula, R1 and R2 are the same or different, Hl-CH
2-CH-CH2, and -CH2\1H elementary atom or chlorine atom, j is an integer from 0 to 5), X is a bromine atom or a chlorine atom,
i is an integer of 0 to 4, preferably 1 to 4, m is 0 to 10
, preferably 1 to 7] and has a bromine atom and/or chlorine atom content of 45 to 60% by weight, preferably 47 to 58% by weight.

Further, the present invention provides the above-mentioned (A) component 20 to 90% by weight and (G) polycarbonate 10 to 80% by weight [However,
Composition 1 consisting of (A) + (G) -100% by weight)
00 parts by weight, 1 to 30 parts by weight of the component (B), 0.05 to 5 parts by weight of the component (C), and 0 to 20 parts by weight of the component (D).
Parts by weight of component (E), 0 to 15 parts by weight of component (E), and 0 to 15 parts by weight of component (F) (hereinafter referred to as "second composition"). The first and second groups of acid compounds are collectively referred to as a "flame-retardant resin composition."

Hereinafter, first, (A) used in the first and second compositions of the present invention.
Component (G) will be explained, and then the first and second compositions will be explained in detail.

Component (A) Component (A) has a grafting rate of 15 to 180% by weight and a copolymerized aromatic vinyl/vinyl cyanide of 50 to 1001
It is a rubber-reinforced styrenic resin having a rubber component content of 5 to 60% by weight.

Examples of the rubbery polymer used in component (A) include diene-based rubbery polymers such as polybutadiene, butadiene-styrene random copolymer, polyisoprene, styrene-butadiene block copolymer, etc. Hydrogenated products thereof, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, acrylic rubber mainly composed of acrylic acid ester, isobutylene-isoprene copolymer, polyurethane rubber, etc. can be used, among others. From the viewpoint of easily obtaining the desired graft ratio, it is preferable to use a diene-based rubbery polymer such as polybutadiene or butadiene-styrene copolymer.
In addition, from the viewpoint of improving light resistance, nyletin-α-
It is preferable to use a hydrogenated product of an olefin-based rubbery copolymer or a diene-based rubbery polymer.

In addition, examples of (co)polymerized aromatic vinyl compounds include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, m-chlorostyrene, p-
Examples include halogen-substituted styrene such as chlorostyrene, and styrene and α-methylstyrene are preferred.

Further, examples of the (co)polymerized vinyl cyanide compound include acrylonitrile and methacrylonitrile.

In addition, (co) in the rubber-reinforced styrene resin of component (A)
The ratio (weight ratio) of the aromatic vinyl compound and vinyl cyanide compound being polymerized is 50 to 10,010 to 50, preferably 60 to 9,515 to 40. If the vinyl cyanide compound exceeds 50, thermal stability will decrease, which is not preferable. Furthermore, when a vinyl cyanide compound is used as an essential component, excellent impact resistance and chemical resistance can be obtained, and especially in a composition using polycarbonate, extremely excellent impact resistance can be obtained.

In addition to the above monomers, other copolymerizable monomers may be used in combination, if necessary. Examples of other monomers include acrylic esters and methacrylic esters, such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.

In addition, other monomers include acrylic acid, methacrylic acid, non-conjugated divinyl compounds represented by divinylbenzene, and polyvalent (meth) compounds such as trimethylolpropane trimethacrylate and trimethylolpropane triacrylate.
One or more acrylate compounds can be used as appropriate so long as they do not affect the polymerization process or the physical properties of the composition of the present invention. The amount of these other monomers used in the monomer mixture is preferably about 50% by weight or less.

The rubber-reinforced styrenic resin of component (A) is a rubber-reinforced styrenic resin obtained by polymerizing an aromatic vinyl compound or an aromatic vinyl compound and a vinyl cyanide compound in the presence of the rubbery polymer. ) or, separately, a (co)polymer obtained by polymerizing an aromatic vinyl compound or an aromatic vinyl compound and a vinyl cyanide compound, and a rubber-reinforced styrenic resin (b) consisting of (a). Of course, as long as the graft ratio, the weight ratio of the (co)polymerized aromatic vinyl compound/cyanated vinyl compound, and the rubbery polymer content are within the range of the present invention, (a) It may consist of (a), (b) and (b), (a) and (b), etc.

The content of the rubbery polymer component in component (A) is 3 to 60% by weight, preferably 5 to 40% by weight.

If the content is less than 3% by weight, the desired impact resistance cannot be obtained, while if it exceeds 60% by weight, flame retardancy and practical moldability will deteriorate, which is undesirable.

In addition, the ratio (graph) in component (A) is 15 to 180% by weight, preferably 30 to 150% by weight, and the kraft ratio is 15% by weight.
If it is less than 120% by weight, the impact resistance will decrease, while if it exceeds 120% by weight, the surface gloss of the molded article will tend to decrease and the heat resistance will tend to decrease, which is not preferable.

Furthermore, the intrinsic viscosity of the methyl ethyl ketone soluble component in component (A) is preferably from 0.3 to 0.8/g, more preferably from 0.35 to 0.7/g. Within this range, a flame-retardant resin composition with a good balance between impact resistance and practical moldability can be obtained.

As a method for producing component (A), known methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization may be used.

At this time, the intrinsic viscosity of the methyl ethyl ketone soluble component can be adjusted by appropriately selecting the type and amount of the molecular weight regulator during polymerization. In addition, regarding the graft rate,
It is possible to adjust the molecular weight by appropriately selecting the type and amount of the molecular weight regulator, as well as the time for adding the monomer component (monomer mixture) to the polymerization system.

Component (B) Component (B) is a halogen-containing compound represented by the above general formula (I).

The halogen-containing compound preferably has a softening point of 112 to 17.
The temperature is 0°C, more preferably 112°C to 150°C, and the preferred weight average molecular weight is 500° to 6°000, still more preferably 1,200 to 4,000.

As for component (B), preferably R1 and R2 in general formula (I) are -CH2-CH-CH2, \1H, and X and Y are bromine atoms.

For a general explanation of the halogen-containing compound (B) represented by the general formula (I), see, for example, JP-A-61-24
This is described in detail in Japanese Patent No. 1322 and the like.

When the softening point of component (B) is 112°C or higher, it is easy to obtain a product with excellent heat resistance, while when it is 117°C or lower, a product with excellent impact resistance is easily obtained.

In addition, when the weight average molecular weight of component (B) is 500 or more,
It is easy to obtain a product with excellent thermal stability during molding processing, and on the other hand, when it exceeds 6,000, the dispersibility in the resin component becomes good and it is easy to obtain a product with excellent impact resistance strength.

Furthermore, if the bromine atom and/or chlorine atom content of component (B) is less than 45% by weight, a large amount is required to obtain the desired flame retardance, and impact strength inevitably decreases. On the other hand, if it exceeds 60% by weight, the thermal stability and light resistance during molding will decrease.

The flame-retardant resin composition of component (C) is required to be used at high temperatures in the molding process due to the development of new applications and improvement of productivity in molding processability, or in the production process at high temperatures in the heating cylinder of the molding machine. Molded products molded under these conditions suffer from poor thermal stability phenomena such as discoloration and sintering, and improvements are desired.

The flame-retardant resin composition of the present invention that does not use component (C) has excellent light resistance, heat resistance, and thermal stability compared to conventional flame-retardant resin compositions. When molded under the molding conditions, the thermal stability is still insufficient.

However, when a phosphite compound as component (C) is used, the above-mentioned thermal stability is significantly improved.

Examples of phosphite compounds include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, l.
, 4-di-t-butylphenyl) bosphite and other aromatic and aliphatic phosphites; diphenyl monodecyl and diphenyl mono(tridecyl) phosphite; Phosphite ester, tetraphenyl dipropylene glycol diphosphite, distearyl pentaerythritol diphosphite, ditridecyl pentaerythritol diphosphite,
Diphosphites such as dinonylphenylpentaerythritol diphosphite, tetra(tridecyl)4,4'-isopropylidene diphenyl diphosphite, and bis(2゜4-di-t-butylphenyl)pentaerythritol diphosphite, etc. be. Preferred are distearyl pentaerythritol diphosphite and bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite.

Component (D) Component (D) is a halogenated bisphenol compound [excluding component (C)], such as tetrabromobisphenol A1, tetrabromobisphenol S, and preferably tetrabromobisphenol A. It is.

Using component (D), without sacrificing flame retardancy,
Practical moldability and impact resistance can be further improved.

Component (E) Component (E) is a halogenated polyolefin, such as chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated ethylene propylene copolymer, and the like. Among these are chlorinated polyethylene,
Chlorinated polyolefins such as chlorinated polypropylene, especially chlorinated polyethylene are preferred. The halogen content in these halogenated polyolefins is preferably 20 to 50% by weight, particularly 25 to 45% by weight.

By using component (E), flame retardance, light resistance, and impact resistance can be improved.

Component (F) Component (F) is an antimony compound, such as antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony phosphate, etc. Preferably, antimony dioxide or sodium antimonate is used. be.

When component (F) is used, much better flame retardancy can be obtained.

(G) Component (G) Component polycarbonate includes, for example, aromatic polycarbonate, aliphatic polycarbonate, aliphatic polycarbonate, and aliphatic polycarbonate.
Aromatic polycarbonate 1. etc. can be mentioned.

(G) Polycarbonate is generally 2,2-bis(4
It is a (co)polymer consisting of bisphenols such as -oxyphenyl) alkanes, bis(4-oxyphenyl) ethers, bis(4-oxyphenyl)sulfone sulfides, or sulfoxides, and can be modified with halogen depending on the purpose. It may also be a (co)polymer using substituted bisphenols.

(G) Regarding types of polycarbonate and manufacturing methods,
■Published by Shikogyo Shimbun (September 30, 1960) “
Polycarbonate 1/Resin”.

This component (G) can improve the heat resistance and impact resistance of the resulting composition.

Next, the eleventh composition of the present invention will be explained.

Eleventh Composition The first composition contains, based on 100 parts by weight of component (A,),
Component (B) 1 to 30 parts by weight, preferably 3 to 25 parts by weight, component (C) 0.05 to 5 parts by weight, preferably 0.1 to 25 parts by weight.
4 parts by weight, 0 to 20 parts by weight of component (D), preferably 0 to 20 parts by weight
15 parts by weight, particularly preferably 0. 5 to 15 parts by weight, (
E) component 0 to 15 parts by weight, preferably 0 to 10 parts by weight,
Particularly preferably 0.5 to 10 parts by weight, component (F) 0 to 1
The flame retardant resin composition contains 5 parts by weight, preferably 0 to 10 parts by weight, particularly preferably 0.5 to 10 parts by weight.

If the amount of component (B) is less than 1 part by weight per 100 parts by weight of component (A), flame retardancy and heat resistance will decrease;
If it exceeds 0 parts by weight, practical moldability and impact resistance will deteriorate, which is not preferable.

Furthermore, component (C) (phosphite ester compound) is (
A) 0.05 to 5 parts by weight per 100 parts by weight of component,
The amount is preferably 0.1 to 1.0 parts by weight, and if it is less than 0.5 parts by weight, the improvement in thermal stability is insufficient, while if it exceeds 5 parts by weight, an improvement effect commensurate with the amount added can be obtained. In addition, heat resistance decreases.

Furthermore, if the amount of component (D) (halogenated bisphenol compound) exceeds 20 parts by weight based on 100 parts by weight of component (A), light resistance and heat resistance decrease, which is not preferable.

Furthermore, component (E) (halogenated polyolefin) or (
A) If the amount exceeds 10 parts by weight per 100 parts by weight of the component,
This is not preferred because thermal stability and heat resistance decrease.

Furthermore, if the amount of component (F) (antimony compound) exceeds 10 parts by weight based on 100 parts by weight of component (A), impact resistance decreases, which is not preferable.

Second composition The second composition consists of (A) component/(G) component -20 to 90/
10-80% by weight, preferably 30-80/20-70
Weight% [folded, (A) + (G) - 100% by weight]
1 to 30 parts by weight of component (B), preferably 3 to 25 parts by weight, and 0.05 to 5 parts by weight of component (C), preferably 0.1 to 4 parts by weight, per 100 parts by weight of the resin composition consisting of Department,
(D) component 0 to 20 parts by weight, preferably 0 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, (E) component 0
~15 parts by weight, preferably 0 to 10 parts by weight, particularly preferably 0.5 to 10 parts by weight, 0 to 15 parts by weight of component (F),
Preferably 0 to 10 parts by weight, particularly preferably 0. 5~
This is a flame retardant resin composition containing 10 parts by weight.

Here, in the resin composition consisting of the (A) component and the (G) component, if the (A) component is less than 20% by weight, the impact resistance and flame retardance will decrease, while if it exceeds 90% by weight. and,
This is not preferred because the modulus, hardness and flame retardancy are reduced.

In a resin composition consisting of components (A) and (G), (G)
If the amount of the component is less than 10% by weight, heat resistance and impact resistance will decrease, while if it exceeds 80% by weight, practical moldability will decrease, which is not preferable.

In addition, component (B), component (C), and (E) in the second composition.
The ingredients, the ratio of the ingredient (F) used, and the reasons thereof are the same as those described for the first composition.

Flame-retardant resin compositions of the present invention (1st and 2nd compositions)
Stabilizers, lubricants, and the like can be added to the composition.

That is, when a small amount of an epoxy compound, an organic tin compound, stearic acid, etc. is added as a stabilizer, the thermal stability during molding is further improved. Addition of a small amount of hydrogenated castor oil, low molecular weight polyethylene, silicone oil, etc. as a lubricant improves moldability.

In order to improve heat resistance and rigidity, the flame retardant resin composition of the present invention may contain fibrous substances such as glass fibers, potassium titanate fibers, ceramic fibers, and metal fillers, as well as talc, calcium carbonate, and titanium oxide. Fillers such as barium sulfate, calcium oxide, aluminum oxide, mica, glass beads, glass flakes, etc. can also be added.

Among these fillers, the heat-resistant fiber and rigidity of the fibrous substance improve as the amount added increases, but the moldability decreases. The amount added to obtain practical moldability is determined according to the first aspect of the present invention.
In the composition, 2 to 70 parts by weight, preferably 5 to 60 parts by weight, per 100 parts by weight of component (A), and in the second composition, per 100 parts by weight of the total of components (A) and (G). be.

The flame-retardant resin composition of the present invention also contains ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and succinate compounds, antioxidants such as hindered phenol compounds, dispersants, blowing agents, and colorants. Flame retardants other than those used in the present invention can also be added as additives.

Method for producing a flame-retardant resin composition of the present invention The flame-retardant resin compositions (compositions 1 and 2) of the present invention are manufactured using no known method for producing a resin composition, except for blending the above-mentioned ingredients. It can be manufactured without any changes.

That is, it can be produced by mixing the above-mentioned components and other necessary additives using a commonly used Henschel mixer, tumbler, etc., and melt-mixing using a heated roll, extruder, Banbury mixer, etc. It is also possible to mix by a so-called masterbatch method, in which a masterbatch in which the above-mentioned components are blended at a high concentration is prepared in advance, and this is blended with the unblended components.

In addition, in the present invention, in the second composition (A) and (G
Although it is defined as a resin composition consisting of the following components, it is also possible to prepare a resin composition by mixing each of these components at the same time, or by separately mixing each of these components with other components. Needless to say.

The flame-retardant resin composition of the present invention is subsequently molded into molded products by extrusion molding, injection molding, compression molding, etc., and these molded products have not only mechanical properties but also flame retardancy and heat resistance. It also has excellent light resistance, practical moldability, and impact resistance, and has a good surface appearance, making it extremely useful as mechanical parts, electrical parts, and automobile parts.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Note that parts and percentages in the examples are each based on weight.

Furthermore, the methods for measuring the graft ratio and intrinsic viscosity and the evaluation of the physical properties of the obtained composition are as follows.

■ Measurement of graft ratio A certain amount (X) of the graft copolymer was placed in acetone and shaken for 2 hours to dissolve the ungrafted (co)polymer component in the graft copolymer into acetone. let

Then, using a centrifuge, the solution (eluate) was diluted with
．． Centrifuge at 30 rpm for 30 minutes to obtain insoluble matter. Next, the insoluble matter was removed at 120°C using a vacuum dryer.
After drying for a period of time, an insoluble fraction (Y) was obtained, which was calculated using the following formula.

C(Y)-(X))
It was measured using an Ubbelohde viscometer under a temperature condition of 30'C.

■Flammability test (flammability) Compliant with UL94.

Test piece; 1/8'xl/2'x5''' and 1/8'xl/2'x5'''
16"XI/2'
1 with a conical tip on a 2.4 mm thick plate placed on top
A 50cm striking rod with a diameter of 2.7mm and a load of 10.56kg
The falling weight impact strength was measured by dropping it from a height of .

■ Practical formability (fluidity) In order to evaluate practical processability, a spiral mold (2 mm thick x 20 mm wide, gate 2 x 3 mm) was used to
oz injection molding machine with molding temperature of 220°C and injection pressure of 8
Flow length (cm) when molded under the condition of 40 kg/c4
) was sought.

■Heat resistance Compliant with ASTM D648.

Test piece; 1/2"XI/2"X5"load; 18.
6kg/c ■ Light resistance Test 100 using a xenon weather meter
Color difference after time (black panel temperature 63℃, no rain) (
ΔE) was calculated using the following formula.

8E-(LOL) 2+(ao-8) 2+ (bo
b) 2LD% aO-bO: Brightness, redness, yellowness of test piece before light resistance test, a, b
; The lightness, redness, and yellowness of the test piece after the lightfastness test. The smaller the ΔE, the better the lightfastness test.

■ Heat-stable flame-retardant resin composition is placed in the cylinder of an injection molding machine at 260°C.
The color difference of the molded product after being retained at 115 minutes at °C was measured based on the molded product before the retention, and the color difference was calculated in the same manner as 8E of light resistance, and evaluated using the following values.

◎ ΔE O~2 0 ΔE 2~5 × 8E > 5 Silpers leakage; ○ is almost none or none × Yes Reference example (preparation of each component) Preparation of graft copolymer Preparation of polybutadiene latex Polymerization was carried out by emulsion polymerization in the presence of styrene, acrylonitrile, and polymerization chemicals to obtain the graft copolymers shown in Table 1.

Preparation of copolymer The copolymers shown in Table 2 were obtained by bulk polymerization using styrene, acrylonitrile, and polymerization chemicals.

Preparation of halogen-containing compound B-1 = The following compound obtained by heating and reacting tetrabromobisphenol A diglycidyl ether (epoxy i372) with tetrabromobisphenol A.

Br CH3Br 0-CH2-CH-CH2) H Br CH3Br R1 and R2; -CH2-CH-CF3X 1 m; about 1.7 Softening point: 118°C Weight average molecular weight: about 2. 600 Bromine content; % B-2: The following compound obtained by heating and reacting tetrabromobisphenol A diglycidyl ether (epoxy equivalent: 372), tetrabromobisphenol A, and tribromobisphenol.

Br CH3Br 0-CH2-CH-CH2]□ H Br CH3Br R1 and R2; Br m; approximately 2.8 Softening point; 140°C Weight average molecular weight; approximately 3. 700 Bromine content: 55% Phosphite ester compound C-1 = distearyl pentaerythritol diphosphite (manufactured by Adeka Argus Chemical ■, MARK PEP-
8) C-2: cyclic pentanetetryrubis (2,4
-dibutylphenyl phosphite) (manufactured by Adeka Argus Chemical ■, MARK PEP'-24) (comparison) C-3 = dibutyltin arate (manufactured by Mitsubishi Organic Synthesis ■, S
t ann RC-20O8) (D) component,
Tetrabromobisphenol A (TBA) was used.

Preparation of component (E) As component (E), 0235 (chlorine content 35%) manufactured by Daiso Co., Ltd. was used.

(F) Preparation of ingredients Antimony trioxide was used as component (F).

(G) Preparation of ingredients (G) As ingredients, Idemitsu Petrochemical Co., Ltd., Taflon FN2
200 (weight average molecular weight 23,000) was used.

Examples 1 to 15, Comparative Examples 1 to 8 The formulations shown in Table 3 were mixed using a Henschel mixer, and 200
Pellets were prepared by melt-kneading at ~230°C. Using this pellet, various physical properties were evaluated. The results are also shown in Table 3.

As is clear from Table 3, Examples 1 to 15 are flame-retardant resin compositions of the present invention, and object 1 of the present invention was obtained.

On the other hand, both Comparative Example 1 and Comparative Example 6 (C
This is an example in which the amount of the phosphite compound (component ) used is less than the range of the present invention, and the thermal stability is poor.

Comparative Example 2 and Comparative Example 7 in which component (G) was added are both examples in which the phosphite compound of component (C) exceeds the scope of the present invention, and the thermal stability and heat resistance are poor.

Comparative Example 3 is an example in which dibutyltin male-1, which is known as a stabilizer and is outside the scope of the present invention, was used in place of the phosphite compound of component (C), but the thermal stability was poor. .

Comparative Example 4 is an example in which the flame retardant of component (B) is less than the range of the present invention, and the flame retardance is poor.

Comparative Example 5 is an example in which the flame retardant of component (B) exceeds the scope of the present invention, and the thermal stability and heat resistance are poor.

Comparative Example 8 is an example in which a flame retardant TBA outside the scope of the present invention was used in place of the flame retardant component (B), and the thermal stability and heat resistance were poor.

[Effect of the invention] Since the flame-retardant resin composition of the present invention uses a specific flame retardant, it has better light resistance, heat resistance, practical moldability, and impact resistance than conventional flame-retardant resin compositions. It has a high balance of physical properties such as flame retardancy and flame retardancy, and contains a phosphite compound, so it can be molded at high molding temperatures or after staying in a high temperature cylinder for a long time. Discoloration of molded products and occurrence of silver streaks are significantly improved.

Conventional flame-retardant resin compositions have poor thermal stability, which has been a major hindrance to improving molding productivity and developing new applications, but the flame-retardant resin composition of the present invention has poor thermal stability. Because of its excellent properties, it can be expected to improve productivity and develop new applications. Therefore, the industrial value is extremely large.

Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] (1) (A) Grafting rate 15-180% by weight, copolymerized aromatic vinyl/vinyl cyanide 50-100/0
to 50% by weight and rubber component content of 5 to 60% by weight of a rubber reinforced styrenic resin, (B) 1 to 30 parts by weight of a halogen-containing compound represented by the following general formula (I) (C) Phosphite ester compound 0.05 to 5 parts by weight (D) Halogenated bisphenol compound [However, (B
A flame-retardant resin composition characterized by containing 0 to 20 parts by weight (E) 0 to 15 parts by weight of a halogenated polyolefin (F) 0 to 15 parts by weight of an antimony compound. (B) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・・・・・・・・・・・・・・・・(I)
[In the formula, R^1 and R^2 are the same or different, -H
, ▲Mathematical formulas, chemical formulas, tables, etc.▼, and -CH_
2 ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (where Y is a bromine atom or chlorine atom, j is an integer from 0 to 5), X is a bromine atom or a chlorine atom, i
is an integer of 0 to 4, and m is an integer of 0 to 10.] A halogen-containing compound having a bromine atom and/or chlorine atom content of 45 to 60% by weight. (2) Composition 10 comprising 20 to 90% by weight of component (A) according to claim 1 and 10 to 80% by weight of (G) polycarbonate [provided that (A) + (G) = 100% by weight]
Component (B) in claim (1) 1 to 30 per 0 parts by weight
parts by weight, component (C) 0.05 to 5 parts by weight, component (D) 0
~20 parts by weight, 0 to 15 parts by weight of component (E), and (F
) A flame-retardant resin composition containing 0 to 15 parts by weight of the component.